Download Transition Metals and Complex Ion Chemistry - Ars

Transition Metals and Complex Ion Chemistry
Definitions
Complex ion - a metal ion with Lewis bases attached to it through coordinate covalent bonds.
A Complex (or Coordination compound) is a compound consisting either of complex ions with other ions of opposite
charge or a neutral complex species.
Ligand - the Lewis bases attached to the metal ion in a complex. Lewis bases are electron pair donors. They can be
ions or neutral molecules. Anions are the most common ionic Lewis bases. Cations only very rarely form ligands with
metal ions because the electron pair is usually held in place by the positive charge.
Coordination number - the total number of bonds Um metal forms with ligands. The most common coordination
number is 6, although 4 is somewhat common also. Complex ions with coordination number of 2 through 8 are known.
Monodentate - ligand that bonds through one of its atoms to the metal ion. (e.g. H2O, NH3, CO, CN-)
Bidentate - ligand that bonds through two of its atoms with the metal Ion. (e.g., C2O42- , ethylenediamine (C2H8N2)
represented as "en")
Polydentate - ligand that bonds through two or more of its atoms to the metal ion. (e.g. EDTA)
Chelate - a complex formed from polydentate ligands.
Bonding in complex ions.
Fe2+ + :NH3 ¾ Fe: NH32+
Or
Fe2+ + (: CòN:)- Ž [ Fe: CòN:]+
Note that the charge on the complex is the sum of the charges of the ions from which it is formed.
Nomenclature of Complex ions
The name of the complex ion tells everything there is to know about the ion.
1. When you are naming a salt the name of the cation goes first. (No change from anything here.)
2. The name of the complex - anion, cation, or neutral - consists of 2 parts. The first part identifies the ligand and the
second part identifies the metal.
3. The complete name consists of a Greek prefix indicating the number of ligands followed by the name of the ligand. If
there is more than one ligand they are named in alphabetical order (ignoring the prefix).
a. anion ligands end in "-o."
ANION NAME
bromide
cyanide
oxalate
LIGAND NAME
bromo
cyano
oxalato,
b. neutral ligands are given the name of the molecule except:
ammonia
carbon dioxide
water
ammine
carbonyl
aqua (older form is "aquo")
c. the prefixes are
1
2
3
4
5
6
et cetera
mono
di
tri
tetra
penta
hexa
d. when the prefix is part of the name of the compound the number of ligands is denoted by "bis" (2), "tris" (3), "tetrakis"
(4). The name of the ligand follows in parenthesis.
4. The complete metal name consists of the name of the metal followed by "-ate" if it is an anion followed by the
oxidation state of the metal in Roman numerals in parenthesis. When there is a Latin name of the metal it is used to
identify the metal in the anions (Except Hg).
Copper
Gold
Iron
Lead
Silver
Tin
cuprum
aurum
ferrum
plumbum
argentum
stannum
cuprate
aurate
ferrate
plumbate
argentate
stannate.
Name the following
Cu(NH3)2(H2O)22+
diamminediaquacopper(II)
[Co(H2O)2(en)2](SO4)3 diaquabis(ethylenediamine)cobalt(VI) sulfate
K2[Ni(CN)4]
MnO4-
potassium tetracyanonickelate(II)
tetraoxomanganate(VII)
What data do we use to determine the geometry and bonding of the complex ions?
1.
Isomerism - these are compounds with the same chemical formula but different arrangements of atoms.
Because the atoms are arranged differently, the compounds have different chemical formulas.
2.
Paramagnetism - indicates the number of unpaired electrons in the compound. This gives information about the
bonding in the compound.
3.
Color - the color absorbed gives information about the electronic structure of the compound.
Isomerism
Structural isomerism - isomers that differ in how the atoms are connected.
Stereoisomers - isomers in which the atoms are connected in the same order but have a different arrangement in
space.
Structural isomers
Ionization isomers - differ in the anion which is bonded to the metal
[CO(NH3)5(SO4)]Br (red)
[CO(NH3)5Br]SO4 (Violet)
Hydrate isomers - differ in the placement of water molecules
[Cr(H2O)6]Cl3 (violet)
[Cr(H2O)5Cl]Cl2½H20(light green)
Coordination isomers - differ in the distribution of ligands between metal ions in complex compounds
[Cu(NH3)4][PtCl4]
[Pt(NH3)4][CuCl4]
Linkage isomers - differ in the atom of the ligand that is bonded to the metal
[Mn(CO)5(SCN)]
[Mn(CO)5(NCS)]
Stereoisomers
Geometric isomers - isomers where the atoms are bonded in the same way but differ because some atoms occupy
different relative positions in space.
Cisplatin (diamminedichloroplatinum(II)) two compounds are known with this composition. One is orange yellow and is
somewhat soluble in water and acts as a cancer-fighting drug. The other is yellow and is much less soluble and doesn't
have the cancer fighting ability.
With four ligands there are two possibilities for the structure; tetrahedral and square planar. Which is this compound?
Cl
Pt
NH3
Cl
NH3
If it were tetrahedral there would be no geometric isomers.
With a square planar geometry there are two
geometric isomers:
Cl
NH 3
Pt
Cl
Cl
NH 3
NH 3
Pt
NH3
Cl
One of these isomers is denoted trans (the one that has the same ligand on opposite sides of the complex. The other is
denoted cis. One is soluble. The complex that is polar is soluble.
Six coordinate compounds (with octahedral geometry) are also capable of geometric isomers.
NH 3 C l NH
3
Co
NH 3
C l NH3
NH3
NH 3
Co
NH3 Cl
NH3
Cl
The cis isomer is purple and the trans isomer is green.
Also
N
N
Cl
Co
Cl
N
N
N N Cl
Co
N
Cl N
The trans isomer is green and the 2 cis isomers are violet.
N N Cl
Co
N
Cl N
The 2 cis isomers are known as optical isomers or enantiomers. Enantiomers are isomers that are non-superimposable
mirror images of each other. In a symmetrical environment the two isomers have the same physical properties
(solubilities, melting points, colors). They can be distinguished by how they rotate plane polarized light. Because of this
they are also known as optically active compounds. Is the compound rotates light to the right it is called dextrorotary
and is labeled “d”. A compound that rotates light to the left is called levorotary and is labeled “l”. A chemical reaction
usually produces a mixture of these two compounds (an exception is biochemical reaction, which produce only one
form). The mixture is called racemic. A racemic mixture can be separated or resolved by making a salt with an
optically active ion of the opposite charge.
Valence Bond Theory of Complexes
Octahedral complexes
Cr3+
all complexes of this ion have six ligands (octahedral geometry) and are paramagnetic indicating 3 unpaired electrons.
The electron configuration of this ion is
[Ar] 3d3
[Ar] æææçç
Let's look at the hexaquacobalt(III) ion. If all of the water molecules bond to the Cr3+ ion we will need 6 hybrid orbitals.
We can use the 4s and 4p orbitals and either two of the 3d orbitals or 2 of the 4d orbitals. Because the 3d orbitals are
lower in energy than the 4d we use those orbitals. This gives a hybridization of d2sp3 (the d first indicates that the d
orbitals come from the energy level 1 lower than the s and p orbitals).
Now look at the hexammineiron(II) ion. The iron ion has an electron configuration of:
[Ar] 3d6
[Ar] åææææ
Using the same argument as above we would have a hybridization Of sp3d2. But what about a complex like the
hexacyanoferrate(II) ion? This is a diamagnetic ion so all of the electrons are paired up. In this case we use the excited
state of the iron(II) ion which has the orbital diagram of åååçç. Now 2 of the 3d orbitals are empty so the
hybridization here would be the same as the chromium complex, d2sp3. This indicates that there are two kinds of
complexes possible. One in which there is a minimum of pairing of electrons, which is known as a high-spin complex.
The other is a low-spin complex, which has more pairing of electrons than in a high-spin complex.
High-spin
Low-spin
weakly bonding ligands.
strongly bonding ligands.
Ions with d1, d2, or d3 configurations form only one spin type of octahedral complex (d2sp). Ions with configurations of
d8 and d9 are similar (sp3d2).
Tetrahedral and square planar complexes
The coordination number 4 is almost as common as 6 (octahedral complexes). Here the geometries are either
tetrahedral or square planar.
sp3
dsp2
Tetrahedral
Square planar
Ni(CN)4- is square planar (evidence is from the fact that it is diamagnetic). Ni2+ has an electron configuration of [Ar] 3d8
and its orbital diagram is (in this case it is the excited state of Ni2+) ååååç so the 3d, 4s, and 3-4p orbitals are
available for hybridization, which results in the hybridization dsp2.
CRYSTAL FIELD THEORY
VB theory explains the bonding and magnetism but it doesn't explain why the complexes are largely colored. Crystal
field theory takes care of this. The theory looks at the effect of the ligands on the d orbitals of the ion. (Review d
orbitals).
Octahedral field on the orbitals
The ligands approach the metal ion along the +/- x, y, and z axes. The ligands are represented by negative point charges
if they are anions and partial negative point charges if they are neutral. The electrons in the d orbitals are going to be
repelled by the negative charges, which alter the energy levels of the orbital. However, the amount by which it is altered
depends on whether the charge approaches the orbital head on (more repulsion) or at an angle (less repulsion). The dz2
and the dx2-y2 orbitals point along the Cartesian axes. The others (dxy, dyz, and dxz) do not point along the Cartesian
axes. The first two are repelled more, which raises their energy level. The last three are also repelled but less which
raises their energy level also but not as much.
______
_______
________
_______
_______
The separation between the two levels is given the symbol, ∆, and is called the crystal field splitting.
Back to high-spin and low-spin complexes. The difference between the two is related to ∆ and another energy, the
pairing energy, P. If the pairing energy is greater than ∆, the electrons are not going to pair up. This leads to a high-spin
complex. If P<∆, we have a situation where it is more likely for electrons to pair up than to go into higher energy levels
and we have a low-spin complex.
Which ligands lead to which spin type?? Those that bond strongly will give a larger ∆ and lead to a low-spin complex.
Those that bond weakly will give a smaller ∆ and a high-spin complex. The spectrochemical series orders the ligands
according to the ∆ they generate.
weakly bonding
strongly bonding
I <Br <CI <F <OH <H20<NH3<en<NO2-<CN- <CO
increasing ∆ Ž
Tetrahedral complexes.
In a tetrahedral complex we have an energy level diagram inverted from that of the octahedral complexes.
______
_______
______
______
______
However, ∆ is smaller here than in the octahedral complexes. This means that only high-spin complexes are observed
(P>A).
The square planar energy level diagram is
______
dx2-y2
______
dxy
______
dz2
______
dxz
______
dyz
Since the ∆ here is much larger overall, we have only low-spin complexes (P<∆).
Visible spectra of complexes
Related to ∆: ∆ = hv = hc/Í
Unlike atomic spectra the complex ions absorb in broader bands. This is due to the changes in the nuclear motion that
result from the changes in the electron occupation of the energy levels.
If ∆ is a large value, the wavelengths that are absorbed are the shorter wavelength (blues and violets). This means that
we would see the complimentary color (reds, yellows, and oranges).
If ∆ is a small value, the reds and yellows are absorbed. We would see the blues and violets.